Novel detergent compositions



3,310,498 NOVEL DETERGENT COMPOSITIONS Edwin E. Michaels, Stamford, and Clayton A. Wetmore,

Norwa'ik, Conn., assignors to Stamford Chemical Industries, Inn, Cincinnati, Ohio, a corporation of Ohio No Drawing. Filed duly 26, 1953, Ser. No. 297,953 6 Claims. (Cl. 252-152) The present invention relates to novel detergent compositions. More particularly, it relates to a detergent composition adapted for incorporation into a highly polar organic drycleaning solvent comprising alkali metal mahogany sulfonates and certain alkanol amine salts of alkyl aryl sulfonic acids.

In the prior practice, mahogany sulfonates have been employed to improve drycleaning solvents, such as Stoddard solvent orperchloroethylene. Improved detergency v and soil dispersion properties of the latter solvents have 'latters eflectiveness, such a product would be highly desirable.

It is an object of this invention to provide a detergent additive composition which exhibits both enhanced detersiveness and water-solubilizing or water-binding properties. It is a further object of the invention to provide an improved mahogany sulfonate additive to drycleaning solvents. Other objects and advantages will become apparent from the detailed description following.

It has been found that the objects stated above can be achieved by incorporating into a polar organic drycleaning solvent a mixture of a polyalkanol amine salt of an alkyl aryl sulfonic acid and an alkali metal or alkaline earth metal salt of a mahogany sulfonate having a molecular weight above about 425. Surprisingly, mixtures prepared as hereinbelow specified, exhibit both enhanced detergency and water-binding properties.

According to the invention, neutralization of an alkyl aryl sulfonic acid with an alkanol amine is performed in the presence of the alkali metal salt of an oil-soluble mahogany sulfonic acid or alkaline earth' metal of an oil-soluble mahogany sulfonic acid. Surprisingly, the desired result cannot be realized where the neutraliza tion of an alkyl aryl sulfonic acid is performed in the absence of a mahogany sulfonate prior to admixture with the latter. It has been further found that from one part of the alkali metal-or alkaline earth metal mahogany sulfonate to from about one-half to about one-and one half on a weight basis, of the amine salt, and preferably an equal weight mixture of each, is suflicient as a good operating practice.

In general, any commercially available oil-soluble mahogany sulfona'te having an average molecular weight of at least 425 can be employed herein. It is advantageous to employ the alkali metal salt of mahogany sulfonic acid, such as the sodium, potassium or lithuim salt thereof, although the alkaline earth metal salts, such as calcium or barium, may also be so used.

- The higher alkyl aryl sulfonic acid to be amine neutralized can be widely varied. Illustrative acids are:

octyl benzene sulfonic acid, nonyl benzene sulfonic acid, decyl benzene sulfonic acid, undecyl benzene sulfonic acid,

United States Patent dodecyl benzene sulfonic acid,

1 lauryl benzene sulfonic acid,

tridecyl benzene sulfonic acid, myristyl "benzene sulfonic acid, hexadecyl benzene sulfonic acid, octadecyl benzene sulfonic acid, ,B-dodecyl naphthyl sulfonic acid, and ,B-myristyl naphthyl sulfonic acid.

In' general, the alkyl substi'tuent contains from 8 to 18 carbon atoms.

The polyalkanol amines utilized in the neutralization of the alkyl aryl sulfonic acid are illustratively:

diethanol amine, triethanol amine, di-n-propanol amine, di-isopropanol amine, and tributanol amine.

Significantly, monoalkanol amines alone cannot be employed herein since they are substantially incompatible with the polar organic solvent herein employed. These solvents are, for instance, perchloroethylene, trichloroethylene, dichloroethylene, and the like. However, up to about 30% of a monoalkanol amine based on the weight of the polyalkanol amine may be admixed with the latter amine. A good practice is to admix from 5% to about 25 of the monoalkanol amine, based on the weight of the polyalkanol amine for best over all results.

As previously stated, it is an important aspect of the present invention to effect the neutralization of the alkyl aryl sulfonic acid with the aforementioned amine in the presence of the mahogany sulfonate salt. In general, the amine is added to a mixture of the alkylaryl sulfonic acid and the salt of the mahogany sulfonate, until a pH of between 6.5 and 9.5 is obtained, and preferably until a pH between 7.0 and 8.0 is achieved. At this point an amber colored, viscous stable solution is noted. To re duce the viscosity of the resultant solution so that it can be more easily handled, it is a good practice to incorporate a small amount usually up to 25% of an inert organic solvent into the mixture prior to neutralization. Such inert solvent include as illustrative:

perchloroethylene, Stoddard solvent, and deodorized kerosene.

To further illustrate the invention the following illustrative examples of the preferred practices are presented. These are not to be taken as limitative of the invention. Unless otherwise stated, the parts are by weight.

' EXAMPLE 1 EXAMPLE 2 To a suitable reaction mixture is admixed 44 parts of sodium mahogany sulfonate (average molecular wt. 450), 56 parts of perchloroethylene, 44 parts of dodecylbenzene sulfonic acid. Thereafter, 17.5 parts of diethanolamine are slowly added. A terminal pH of 7.4 is observed.

EXAMPLE 3 To a mixture of 44 parts of dodecylbenzenesulfonie acid is added 44 parts of sodium mahogany sulfonate in 56 parts of petroleum ether. Thereafter, 22 parts of triethanol amine are added to the latter resultant mixture. A terminal pH of 7.3 is observed.

EXAMPLE 4 To a suitable reaction vessel are added 21 parts of sodium mahogany sulfonate, 29 parts of perchloroethyl- Table I Percent Detergency Percent Percent Redepositien Wat er Solvent Detergent in Perchloroethylene Soluble R.H.

' Stain Cotton Wool Cotton Wool Removal Sodium Salt of Mahogany Sulfonate .t 20. 5 3 9 10.8 70 Example 1 Detergent 44 6S. 5 0 7. 7 100 Example 2 Detergent 45v 5 73 1. 1 7. 7 100 Example 3 Detergent, 48. 5 G7 0 7. 7 100 70 Example 4 Detergent; 29 46 6. 2 20. 5 100 70 Triethanol Amine salt; of dodecylbenzenesuliouic acid 27.3 23.8 10. 5 20. 9 65 ene, 13.3 parts of tridecylbenzene sulfonic acid. A mixture of amines, i.e., 13 parts of triethanol amine and 2.3 parts of monoisopropanol amines, is then added to the reaction vessel and the contents therein gently admixed for 30 minutes. A terminal pH of 8.1 is noted.

Enhanced detersive properties of the compositions illustrated in the table below are determined in the conventional manner involving the use of a launderorneter as described in the AATCC year book for 1955 at page 55 following. In a typicalrun a standard soiled swatch and stainless steel balls together with the highly polar drycleaning solvent perchloroethylene, containing 1% by weight of the detergent additive mixture are added to a launderometer jar. After a twenty minute wash cycle, the washed swatch is removed from the jar, and dried to remove the solvent. Reflectance readings before and after washing of the soiled and 'unsoiled swatches are taken and recorded in percent detergency and percent redeposition, respectively. In the illustrative examples below, the initial reflectance readings of the cotton and wool swatches used are: 103 and 92, respectively. Percent detergency is determined by subtracting the reflectance reading of the soiled swatch and dividing this difference by the difference between the initial unsoiled swatch reflectance reading and soiled reflectance reading, multiplied by 100. Thus, for instance, the percent detergency for cotton is:

where R is the reflectance reading of unsoiled swatches after drycleaning. In the examples below the percent tdetergency and percent redeposition are determined in perchloroethylene solvent. v

Water binding test procedure is conducted in each of the examples tabulated below as follows:

A visual water tolerance value (V.W.T.V.) of an oil soluble detergent is a measurement of the amount of water that the detergent will hold or otherwise dissolve in solvent, such as perchloroethylene. Water tolerance value herein is obtained by visual measurements in the formula below by adding water to a known amount of detergent dissolved in solvent until the solution shows a definite cloudiness:

amt. of water (in grams) amt. 9f gl etiegent solvent soln. (in cc.) X

percent detergent V.W.T.V.:

From Table I above, it can be readily seen that the overall detersiveness values of the mixture is generally higher than the detersiveness values for the individual components. Advantageously, the compositions of the present invention exhibit synergistic properties with respect to sweet-stain removal.

In Table II below the visual water tolerance values are summarized.

Table II etergentz' V.W.T.V. Sodium mahogany sulfonate 0.67 Example 1 composition in perchloroethylene 2.2 Example 2 composition in perchloroethylcne 1.2 Example 3 composition in perchloroethylene 1.1

It will be seen from the above table that the compositions of the present invention exhibit a markedly higher water binding effect than do the mahogany sulfonates. This property is related directly to the maintenance of a low or safe solvent relative humidity.

We claim:

1. A polar solvent compatible d etergene composition consisting essentially of:

(a) 1 part by weight of an alkali metal oil-soluble mahogany sulfonate having an average molecular weight of at least 425, and

(b) from 0.5 part to 1.5 part of a poly lower alkanol amine salt of a higher alkyl aryl sullonic acid, said amine salt being formed by reacting said poly lower alkanol amine with said higher alkyl aryl sulfonic acid in the presence of said mahogany sulfonate, and the mixture being substantially neutralized to a pH of from about 6.5 to 9.5.

2. A composition according to claim 1 in which the alkali metal oil-soluble mahogany sulfonate is sodium mahogany sulfonate and the poly lower alkanol amine salt is triethanol amine salt of dodecyl benzene sulfonic acid.

3. A polar solvent compatible detergent composition consisting essentially of: I

(a) 1 part of an alkyl metal oil-soluble mahogany s'ulfonate having an average molecular weight of at least 425, i

(b) from 0.5 part to 1.5 parts of a poly lower alkanol amine salt of a higher alkyl aryl sulfonic acid, and

(c) from about 5% to about 30% of a mono lower alkanol amine salt of a higher alkyl aryl sulfonic acid, based on the weight of the said polyalkylanol amine salt, said amine salts (b) and (c) both being formed by reacting both said poly lower alkanol amine and said mono lower alkanol amine with said higher alkyl aryl sulfonic acid in the presence of said mahogany sulfonate, and the mixture being substantially neutralized to a pH from about 6.5 to 9.5.

4. A composition according to claim 9 in which the alkali metal oil-soluble mahogany sulfonate is sodium mahogany sulfonate, the poly lower alkanol amine salt is triethanol amine salt of dodecyl benzene sulfonic acid, and the mono lower alkanol amine salt is isopropanol amine salt of dodecylbenzenesulfonic acid.

5. A process for preparing oil-soluble, detergent composition which consists essentially in the steps of: admixing in the presence of an alkali metal salt of an oil-soluble mahogany sulfonate having an average molecular Weight of at least 425, (a) a higher alkyl aryl sulfonic acid with (b) a poly lower alkanol amine until a pH between 6.5 and 9.5 is obtained and the corresponding amine salt is formed, and the components of the mixture (a) and (b) being in proportion to provide from 0.5 to 1.5 parts of amine salt per part of mahogany sulfonate.

6. The process according to claim 5 in which from about 5% to about 30% of a monoalkanolamine, based on the weight of said poly lower alkanol amine is introduced simultaneously with the latter amine.

References Cited by the Examiner UNITED STATES PATENTS 2,271,635 2/1942 Flett 252-89 2,566,298 9/1951 Irwin 252-153 3,012,969 12/1961 Minne et a1 252-153 3,091,508 5/1963 Edwards 252-89 3,101,240 8/1963 Mathews 8-142 3,163,493 12/1964 Hess 8-142 3,174,935 3/1965 Eccles et a1 252-152 X LEON D. ROSDOL, Primary Examiner.

DONALD E. CZAJA, S. E. DARDEN,

Assistant Examiners. 

1. A POLAR SOLVENT COMPATIBLE DETERGENE COMPOSITION CONSISTING ESSENTIALLY OF: (A) 1 PART BY WEIGHT OF AN ALKALI METAL OIL-SOLUBLE MAHOGANY SULFONATE HAVING AN AVERAGE MOLECULAR WEIGHT OF AT LEAST 425, AND (B) FROM 0.5 PART TO 1.5 PART OF A POLY LOWER ALKANOL AMINE SALT OF A HIGHER ALKYL ARYL SULFONIC ACID, SAID AMINE SALT BEING FORMED BY REACTING SAID POLY LOWER ALKANOL AMINE WITH SAID HIGHER ALKYL ARYL SULFONIC ACID IN THE PRESENCE OF SAID MAHOGANY SULFONATE, AND THE MIXTURE BEING SUBSTANTIALLY NEUTRALIZED TO A PH OF FROM ABOUT 6.5 TO 9.5. 